US2615893A - Preparation of thiocarbamyl thiazyl monosulfides - Google Patents

Preparation of thiocarbamyl thiazyl monosulfides Download PDF

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US2615893A
US2615893A US160592A US16059250A US2615893A US 2615893 A US2615893 A US 2615893A US 160592 A US160592 A US 160592A US 16059250 A US16059250 A US 16059250A US 2615893 A US2615893 A US 2615893A
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disulfide
thiocarbamyl
preparation
thiazyl
monosulfide
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US160592A
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Albert F Hardman
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Wingfoot Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/74—Sulfur atoms substituted by carbon atoms

Definitions

  • This invention relates to a new method for the preparation of thiocarbamyl thiazyl monosul fides, a class of compounds which are useful as accelerators in the vulcanization of rubber.
  • the thiocarbamyl thiazyl monosulfides have been prepared in the past by reacting, for example, a Z-halogen benzothiazole with analkali salt of a dialkyl dithiocarbamate. These reactions were slow and had to be carried out under pressure since the halogen of the zshalogen benzothiazole is not very labile.
  • a thiuram disulfide is reacted with a dithiazyl disulfide in the presence of an alkali metal cyanide to form the thiocarbamyl thiazyl. monosulfide
  • R represents a thiazyl radical
  • R. represents a thiocarbamyl radical
  • M represents an alkali metal radical
  • the method of preparation to which this invention relates embraces the reaction of a member of the class of dithiazyl disulfides with a
  • dithiazyl compounds which may be used in the practice of this invention are dibenzothiazyl disulfide, the substituted benzothiazyls such as G-nitro-benzothiazyl disulfide, -chloro-benzothiazyl disulfide, and 6-chlorobenzothiazyl disulfide, the alkyl thiazyls such as 4,5-dimethyl thiazyl disulfide and 4-ethyl thiazyl disulfide, andnaphthothiazyl disulfide.
  • the thiuram disulfides to which this method of preparation pertains include the tetraalkyl thiuram disulfides such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, the tetra-aromatic compounds such as tetraphenyl thiuram disulfide,
  • the-tetra-aralkyl compounds such as tetrabenzyl thiuram disulfide, the cycloaliphatic' compounds such as tetracyclohexyl thiuram disulfide, and
  • heterocyclic compounds such as dipiperidyl thiuram disulfide and dimorpholyl thiuram disulfide.
  • Any alkali metal cyanide may be ,used in the reaction, such as sodium or potassium cyanide.
  • Sodium cyanide is preferred since it is the cheapest of the materials available commercially.
  • the reaction should take place in solution.
  • the reaction has been found to Work in a Water solution, although an organic solvent is preferred since by providing a reacting medium which dissolves but doesnot chem- I ically affect the reactants, it is possible to obtain a more intimate mixture with resultanthigher conversions and higher yields.
  • the solvent used may be any inert solvent, by which term is meant any solvent for the reacting materials which will not enter into nor chemically affect thereaction. Examples of such solvents are methyl alcohol, ethyl alcohol, isopropyl alcohol, ether, dioxane, acetone, and methyl ethyl ketone.
  • Example 1 Tetraethyl thiuram disulfide 15 grams) and 2,2 dibenzothiazyl disulfide (1'7 grams) were mixed into 50 cubic centimeters of methyl alcohol. .To this mixture were added 6.5 grams of potassium cyanide. The mixture immediately became warm and largely went into solution. The mixture was thenheated on a steam bath until all reactants were in solution. Upon cooling, 20 grams of white crystals were obtained. These crystals melted at to 77 C., and when recrystallized melted at IS-80 C. Analysis showed a sulfur content of 34.42% and 34.59%
  • the calculated sulfur is 34.0% and nitrogen 9.95%.
  • the formula therefore was assumed'to Example 3
  • the 2-benzothiazyl dimethyl thiocarbamyl monosulfide was prepared from 2,2 henzothiazyl disulfide and tetramethyl 'thiura'm'disulfide according to the same procedure as shown in Example 2. The yield was 91%.
  • the pure recrystallized material melted at 121 to 122 C.
  • An analysis showed a sulfur content of 37.19% and 38.05% and a.- nitrogen content of 10.68% and 10.75%.
  • Calculated sulfur is 37.80% and nitrogen 11.03%. i
  • the formula is therefore assumed to be 13.39%.
  • Calculated sulfur is 31.30% and nitrogen 13.70%.
  • Examples of other thiocarbamyl thiazyl monosulfides which may be made according to the practice of this invention are B-cyanoethylethyl thiocarbamyl benzothiazyl-monosulflde, tetra hydrofurfuryl-cyclohexyl-thiocarbamy1- ben'zothiazyl-monosulfide, allyl-ethyl-thiocarbamyl-benzothiazyl-monosulfide, N-cyclotetramethylene thiocarbamyl benzothiazyl-monosulfide, phenyl methyl thiocarbamyl-benzothiazyl monosulfide, diphenyl-thiocarbamylbenzothiazyl-monosulfide, diethyl-thiocarbamyl- 6 nitrobenzothiazyl-monosulfide, methyl-isopropyl
  • a method for the preparation of a thiocarbamyl thiazyl monosulfide which comprises reacting a mixture of a thiazyl disulfide and a thiuram disulfide with an alkali metal cyanide.
  • a method for the preparation of a thiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of a dibenzothiazyl disulfide, and a thiuram disulfide with an alkali metal cyanide.
  • a method for the preparation of a thiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and a tetralkyl thiuram disulfide with an alkali metal cyanide.
  • a method for the preparation of dimethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetramethyl thiuram disulfide with an alkali metal cyanide.
  • a method for the preparation of diethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetraethyl thiuram disulfide with an alkali metal cyanide.
  • a method for the preparation of piperidylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and dipiperidyl thiuram disulfide with an alkali metal cyanide.
  • a method for the preparation of dimethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetramethyl thiuram disulfide with sodium cyanide.
  • a method for the preparation of diethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of-dibenzothiazyl 5 disulfide and tetraethyl thiuram disulfide with sodium cyanide.
  • a method for the preparation of piperidylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and dipiperidyl thiuram disulfide with sodium cyanide.
  • a method for the preparation of dimethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetramethyl thiuram disulfide with sodium cyanide in acetone.
  • a method for the preparation of diethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetraethyl thiuram disulfide with sodium cyanide in acetone.
  • a method for the preparation of piperidylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and dipiperidyl thiuram disulfide with sodium cyanide in acetone.
  • a method for the preparation of beta-cy anoethyl-ethyl thiocarbamyl benzothiazyl mono sulfide which comprises reacting a mixture 01. dibenzothiazyl disulfide and N,N-diethyl-N,N'- dicyanoethyl thiuram disulfide with an alkali metal cyanide.

Description

at atmospheric pressure. provide a method for the preparation of these and the alkali metal thiocyanate. is thought to take place according to the followmember of the'class of thiuram disulfides.
Patented Oct. 28, 1952 PREPARATION OF THIOCARBAMYL THIAZYL MONOSULFIDES Albert F. Hardman, Akron, Ohio, assignor to Wingfoot Corporation, Akron, Ohio, 2, corporation of Delaware No Drawing. Application May 6, 1950, Serial No. 160,592
13 Claims. 1. This invention relates to a new method for the preparation of thiocarbamyl thiazyl monosul fides, a class of compounds which are useful as accelerators in the vulcanization of rubber.
The thiocarbamyl thiazyl monosulfideshave been prepared in the past by reacting, for example, a Z-halogen benzothiazole with analkali salt of a dialkyl dithiocarbamate. These reactions were slow and had to be carried out under pressure since the halogen of the zshalogen benzothiazole is not very labile.
It is an object of this invention to provide a method for the preparation of thiocarbamyl thiazyl monosulfides which may be carried out Another object is to compounds requiring a relatively short reaction time. Still another object is to provide a method for preparing thiocarbamyl thiazyl monosulfides in high yields and in a high degree of purity. Another object is to provide an efficient, inexpensive method for the production of thiocarbamyl thiazyl monosulfides. Further objects will appear as the description proceeds.
According to the practice of this invention, a thiuram disulfide is reacted with a dithiazyl disulfide in the presence of an alkali metal cyanide to form the thiocarbamyl thiazyl. monosulfide The reaction ing equation:
Where R represents a thiazyl radical, R. represents a thiocarbamyl radical and M represents an alkali metal radical.
The method of preparation to which this invention relates embraces the reaction of a member of the class of dithiazyl disulfides with a Examples of the dithiazyl compounds which may be used in the practice of this invention are dibenzothiazyl disulfide, the substituted benzothiazyls such as G-nitro-benzothiazyl disulfide, -chloro-benzothiazyl disulfide, and 6-chlorobenzothiazyl disulfide, the alkyl thiazyls such as 4,5-dimethyl thiazyl disulfide and 4-ethyl thiazyl disulfide, andnaphthothiazyl disulfide. The thiuram disulfides to which this method of preparation pertains include the tetraalkyl thiuram disulfides such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, the tetra-aromatic compounds such as tetraphenyl thiuram disulfide,
.the-tetra-aralkyl compounds such as tetrabenzyl thiuram disulfide, the cycloaliphatic' compounds such as tetracyclohexyl thiuram disulfide, and
the heterocyclic compounds such as dipiperidyl thiuram disulfide and dimorpholyl thiuram disulfide. Any alkali metal cyanide may be ,used in the reaction, such as sodium or potassium cyanide. Sodium cyanide is preferred since it is the cheapest of the materials available commercially.
For best results the reaction should take place in solution. The reaction has been found to Work in a Water solution, although an organic solvent is preferred since by providing a reacting medium which dissolves but doesnot chem- I ically affect the reactants, it is possible to obtain a more intimate mixture with resultanthigher conversions and higher yields. The solvent used may be any inert solvent, by which term is meant any solvent for the reacting materials which will not enter into nor chemically affect thereaction. Examples of such solvents are methyl alcohol, ethyl alcohol, isopropyl alcohol, ether, dioxane, acetone, and methyl ethyl ketone. The practice of this invention is further illustrated by the following examples:
Example 1 Tetraethyl thiuram disulfide 15 grams) and 2,2 dibenzothiazyl disulfide (1'7 grams) were mixed into 50 cubic centimeters of methyl alcohol. .To this mixture were added 6.5 grams of potassium cyanide. The mixture immediately became warm and largely went into solution. The mixture was thenheated on a steam bath until all reactants were in solution. Upon cooling, 20 grams of white crystals were obtained. These crystals melted at to 77 C., and when recrystallized melted at IS-80 C. Analysis showed a sulfur content of 34.42% and 34.59%
and a nitrogen content of 9.66% and 9.77%.
The calculated sulfur is 34.0% and nitrogen 9.95%. The formula therefore was assumed'to Example 3 The 2-benzothiazyl dimethyl thiocarbamyl monosulfide was prepared from 2,2 henzothiazyl disulfide and tetramethyl 'thiura'm'disulfide according to the same procedure as shown in Example 2. The yield was 91%. The pure recrystallized material melted at 121 to 122 C. An analysisshowed a sulfur content of 37.19% and 38.05% and a.- nitrogen content of 10.68% and 10.75%. Calculated sulfur is 37.80% and nitrogen 11.03%. i The formula is therefore assumed to be 13.39%. Calculated sulfur is 31.30% and nitrogen 13.70%. The formula is therefore assumed to be h CzHs )C-*aS-C$h s oimon Example 5 Y N,N dimethy1-N,N' diisopropyl thiuram disulfide (60 grams) and 2,2 diben'zothiaz'yl disulfide (70 grams) were stirred into 160 cubic centimeters of acetone. To this mixture were added 60 cubic centimeters of a 33/;% solution of sodium cyanide by weight in water. Upon cooling, crystals were obtained which when washed and dried melted at 120 to 121 0. Analysis showed a sulfur content of 33.74 and 33.58% and a nitrogen content of 9.85 and 9.82%. Calculated sulfur is 34.00% and nitrogen 9.95%. The formula was therefore assumed to be 6,6'-dinitro benzothiazyl disulfide (22 grams) and tetraethyl thiuram disulfide (15 grams) were stirred into 50 cubic centimeters of a 33 ,575 solution of sodium cyanide by weight in water. In a few minutes crystals formed, which when separated, washed with acetone and dried, melted at 122-123 C. Analysis showed a sulfur content of 28.79 and 28.68% and a nitrogen content of 12.12 and 12.20%. Calculated sulfur is 29.50% and nitrogen 12.85%. The formula therefore was assumed to be N 02H: \CS--C--N O2N \S/ 02H:
Examples of other thiocarbamyl thiazyl monosulfides which may be made according to the practice of this invention are B-cyanoethylethyl thiocarbamyl benzothiazyl-monosulflde, tetra hydrofurfuryl-cyclohexyl-thiocarbamy1- ben'zothiazyl-monosulfide, allyl-ethyl-thiocarbamyl-benzothiazyl-monosulfide, N-cyclotetramethylene thiocarbamyl benzothiazyl-monosulfide, phenyl methyl thiocarbamyl-benzothiazyl monosulfide, diphenyl-thiocarbamylbenzothiazyl-monosulfide, diethyl-thiocarbamyl- 6 nitrobenzothiazyl-monosulfide, methyl-isopropyl thiocarbamyl-benzothiazyl-monosulfide. dimethyl thiocarbamyl 4,5 dimethyl-thiazylmonosulfide, and dimethyl thiocarbamyl 4- ethyl-thiazyl-monosulfide.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
I claim:
1. A method for the preparation of a thiocarbamyl thiazyl monosulfide which comprises reacting a mixture of a thiazyl disulfide and a thiuram disulfide with an alkali metal cyanide.
2. A method for the preparation of a thiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of a dibenzothiazyl disulfide, and a thiuram disulfide with an alkali metal cyanide.
3. A method for the preparation of a thiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and a tetralkyl thiuram disulfide with an alkali metal cyanide.
4. A method for the preparation of dimethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetramethyl thiuram disulfide with an alkali metal cyanide.
5. A method for the preparation of diethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetraethyl thiuram disulfide with an alkali metal cyanide.
6. A method for the preparation of piperidylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and dipiperidyl thiuram disulfide with an alkali metal cyanide.
7. A method for the preparation of dimethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetramethyl thiuram disulfide with sodium cyanide.
8. A method for the preparation of diethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of-dibenzothiazyl 5 disulfide and tetraethyl thiuram disulfide with sodium cyanide.
9. A method for the preparation of piperidylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and dipiperidyl thiuram disulfide with sodium cyanide.
10. A method for the preparation of dimethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetramethyl thiuram disulfide with sodium cyanide in acetone.
11. A method for the preparation of diethylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and tetraethyl thiuram disulfide with sodium cyanide in acetone.
12. A method for the preparation of piperidylthiocarbamyl benzothiazyl monosulfide which comprises reacting a mixture of dibenzothiazyl disulfide and dipiperidyl thiuram disulfide with sodium cyanide in acetone.
13. A method for the preparation of beta-cy anoethyl-ethyl thiocarbamyl benzothiazyl mono sulfide which comprises reacting a mixture 01. dibenzothiazyl disulfide and N,N-diethyl-N,N'- dicyanoethyl thiuram disulfide with an alkali metal cyanide.
ALBERT F. HARDMAN.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,682,920 Maximofi Sept. 4, 1928 1,923,957 Teppema Aug. 22, 1933 2,453,460 Robshaw Nov. 9, 1948 2,499,975 Robshaw Mar. 7, 1950 2,510,893 Kleimann June 6, 1950 OTHER REFERENCES Foss: Chem. Abstracts, v01. 42 (1948), page 2240.

Claims (1)

1. A METHOD FOR THE PREPARATION OF A THIOCARBAMYL THIAZYL MONOSULFIDE WHICH COMPPRISES REACTING A MIXTURE OF A THIAZYL DISULFIDE AND A THIURAM DISULFIED WITH AN ALKALI METAL CYANIDE.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2765277A (en) * 1951-11-21 1956-10-02 Exxon Research Engineering Co Lubricating oil additives

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1682920A (en) * 1926-09-18 1928-09-04 Naugatuck Chem Co Manufacture of thiuram monosulphides
US1923957A (en) * 1927-12-10 1933-08-22 Goodyear Tire & Rubber Accelerator of vulcanization
US2453460A (en) * 1944-05-09 1948-11-09 Monsanto Chemicals Manufacture of tetraalkyl thiuram monosulfide
US2499975A (en) * 1944-05-09 1950-03-07 Monsanto Chemicals Manufacture of organic monosulfides
US2510893A (en) * 1946-12-20 1950-06-06 Velsicol Corp Production of organo-thiyl compounds

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1682920A (en) * 1926-09-18 1928-09-04 Naugatuck Chem Co Manufacture of thiuram monosulphides
US1923957A (en) * 1927-12-10 1933-08-22 Goodyear Tire & Rubber Accelerator of vulcanization
US2453460A (en) * 1944-05-09 1948-11-09 Monsanto Chemicals Manufacture of tetraalkyl thiuram monosulfide
US2499975A (en) * 1944-05-09 1950-03-07 Monsanto Chemicals Manufacture of organic monosulfides
US2510893A (en) * 1946-12-20 1950-06-06 Velsicol Corp Production of organo-thiyl compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2765277A (en) * 1951-11-21 1956-10-02 Exxon Research Engineering Co Lubricating oil additives

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